On January 16, 1937, he was appointed the under-secretary to the Holy and Sacred Synod of the Ecumenical Patriarchate. On March 20, 1938, he was ordained to the holy priesthood at the Church of the Holy Trinity in Pera by Metropolitan Germanos of Sardis.

After his ordination as priest, Father Polyevktos moved to the United States and served as priest in a number of parishes. He first served for four years in Perth Amboy, New Jersey, followed by serving three years at the Church of St. Demetrios in Astoria, New York. While he was at St. Demetrios, Fr. Polyevktos taught at the Holy Cross Theological school then in Pomfret, Connecticut. From 1944 to 1955, Fr. Polyevktos served as the dean of Annunciation Cathedral in San Francisco, California. In addition to his regular responsibilities at the cathedral he hosted a radio program for nine years, published an Orthodox periodical, and founded an institute of Orthodox theology.

On October 11, 1955, Fr. Polyevktos was elected Bishop of Tropaiou by the Holy and Sacred Synod of the Ecumenical Patriarchate and assigned as an auxiliary Bishop to Archbishop Michael the ruling bishop of the Greek Orthodox Archdiocese of North and South America. He was consecrated on November 3, 1955 at St. Nicholas Cathedral in Pittsburgh, Pennsylvania by Abp. Michael and Bps. Theodosios of Eukarpias, Athenagoras of Elaias, and Ezekiel of Nazianzus and assigned to serve as the auxiliary bishop of the Sixth Archdiocesan District in Pittsburgh.

In 1960, Bp. Polyevktos was elevated to Metropolitan and was then transferred to South America, where he served until early 1963. On February 5, 1963, the Holy Synod of Constantinople elected him as the first bishop of the newly created Metropolis of Germany and Exarch of Holland and Denmark. In June 1968, he was elected Metropolitan of Ilioupoleos and Theira, and then in August 1969 he was appointed the first Metropolitan of the new Metropolis of Sweden. In April 1974, Metr. Polyevktos was elected the Metropolitan of Aneon.

Metr. Polyevktos later retired and established his residence in Athens. He reposed peacefully on February 1, 1988.